US7438769B2 - Process for diffusing titanium and nitride into a material having a coating thereon - Google Patents

Process for diffusing titanium and nitride into a material having a coating thereon Download PDF

Info

Publication number
US7438769B2
US7438769B2 US11/405,959 US40595906A US7438769B2 US 7438769 B2 US7438769 B2 US 7438769B2 US 40595906 A US40595906 A US 40595906A US 7438769 B2 US7438769 B2 US 7438769B2
Authority
US
United States
Prior art keywords
coating
base material
titanium
salt bath
sodium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US11/405,959
Other languages
English (en)
Other versions
US20070243398A1 (en
Inventor
Philos Jongho Ko
Bongsub Samuel Ko
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US11/405,959 priority Critical patent/US7438769B2/en
Application filed by Individual filed Critical Individual
Priority to EP07760366A priority patent/EP2007572A4/fr
Priority to CN2007800226294A priority patent/CN101535038B/zh
Priority to KR1020147003959A priority patent/KR101496686B1/ko
Priority to JP2009506686A priority patent/JP2009534534A/ja
Priority to BRPI0710618-1A priority patent/BRPI0710618A2/pt
Priority to MX2008013364A priority patent/MX2008013364A/es
Priority to CA002649232A priority patent/CA2649232A1/fr
Priority to CN201310140402.7A priority patent/CN103215539B/zh
Priority to KR1020087028059A priority patent/KR20090068190A/ko
Priority to PCT/US2007/066291 priority patent/WO2007121157A2/fr
Publication of US20070243398A1 publication Critical patent/US20070243398A1/en
Priority to US12/251,617 priority patent/US20090035481A1/en
Application granted granted Critical
Publication of US7438769B2 publication Critical patent/US7438769B2/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
    • C23C12/02—Diffusion in one step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/14—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by a layer differing constitutionally or physically in different parts, e.g. denser near its faces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
    • C23C10/26—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions more than one element being diffused
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component

Definitions

  • the present invention generally relates to a process for diffusing titanium and nitride into a material. More specifically, a process is provided for diffusing titanium and nitride into a material having a coating thereon.
  • the present invention relates to a low temperature process for diffusing titanium and nitride into a base material having a coating thereon in the presence of electrolyzed titanium.
  • a low temperature process is preferred in that it prevents or lessens warping and twisting of the material.
  • Titanium is considered a generally inert, light-weight material which has very high tensile strength (or toughness) and excellent corrosion resistance. Accordingly, because of their inert nature, increased hardness, increased tensile strength and increased resistance to wear, products containing titanium may be used in various applications including industrial, biomedical, aerospace, automotive, defense, jewelry, tools, tool-making, gun-making applications and other such applications.
  • Various materials are used in applications which require hardness, tensile strength and/or resistance to wear. Although these materials may inherently include these attributes, it is desirable to further enhance such. Accordingly, various surface treatment and coating processes have been applied to these materials.
  • Conventional surface treatment and coating processes may include, but are not limited to, heat treatment, nanocoating, ceramic coating, Physical Vapor Deposition (PVD), Chemical Vapor Deposition (CVD), Ion Assisted Coating (IAC), and other suitable surface treatments or coating. These conventional processes are typically preferred because they extend the life of the material at a lower cost than replacement of such.
  • a coating is only as good as the strength of the bond between the coating and the substrate material. Good adhesion is an important prerequisite in engineering a commercially useful coating process. For this reason, a number of coating processes have been developed, each attempting to improve the interfacial strength between the coating and the base material.
  • conventional surface treatments and coating processes have been typically applied to steel and steel alloys.
  • Steel and steel alloys are generally known to contain a high content of iron.
  • Some conventional surface treatment processes such as in some Physical Vapor Deposition (PVD), Chemical Vapor Deposition (CVD) and Ion Assisted Coating (IAC) processes, involve nitriding, wherein nitrogen is introduced such that it reacts to iron in the steel or steel alloy to form a hardened ferrous nitride layer. This reaction causes the formation of a hardened ferrous nitride layer, which serves as a suitable coating on the base material.
  • PVD Physical Vapor Deposition
  • CVD Chemical Vapor Deposition
  • IAC Ion Assisted Coating
  • nitriding processes are generally deficient when treating materials which contain a relatively low content of iron (e.g., carbide). As such, when applying these processes to such materials, there is generally not enough iron for nitrogen to react with. Accordingly, conventional nitriding surface treatments cannot generally form a hardened ferrous nitride layer on the base material due to its low iron content. Instead, a coating is formed which has a weak adhesion with the base material surface, thereby causing it to be susceptible to chipping.
  • iron e.g., carbide
  • a method for diffusing titanium and nitride into a base material having a coating thereon and products produced thereby are provided.
  • the present invention process allows for the implementation of the enhanced properties of titanium in both the coating and the base material.
  • the base material may be treated using the present invention titanium and nitride diffusion process and then treated with a conventional surface treatment or coating.
  • the method generally includes the steps of providing a base material having a coating thereon; providing a salt bath which includes sodium dioxide and a salt selected from the group consisting of sodium cyanate and potassium cyanate; dispersing metallic titanium formed by electrolysis of a titanium compound, in said bath; heating the salt bath to a temperature ranging from about 430° C. to about 670° C.; and soaking the coated material in the salt bath for a time of from about 10 minutes to about 24 hours.
  • titanium and nitrogen diffuses and fills the voids within the coating structure, while also diffusing and filling in the voids within base material structure. Moreover, the diffusion from the coating en route to the underlying base material forms a resulting titanium interface or network therebetween. This interface or network provides for the added benefit of providing better adhesion between the coating and the underlying base material.
  • a treated article including a base material having a coating thereon, wherein the base material and coating each include a microstructure; a titanium component diffused into each of the microstructures; and the titanium component is in addition to any titanium present in each of the coating and the base material.
  • a treated article comprising a treated base material having a particular microstructure; a titanium component diffused into the microstructure; and the titanium component is in addition to any titanium present in the base material.
  • the base material may be treated with a conventional surface treatment or coating after being treated using the present invention titanium and nitride diffusion process.
  • the method generally includes the steps of providing a base material; providing a salt bath which includes sodium dioxide and a salt selected from the group consisting of sodium cyanate and potassium cyanate; dispersing metallic titanium formed by electrolysis of a titanium compound, in said bath; heating the salt bath to a temperature ranging from about 430° C. to about 670° C.; soaking the base material in the salt bath for a time of from about 10 minutes to about 24 hours; and treating the base material.
  • the coating of the base material may be formed using a process selected from the group consisting of heat treatment, nanocoating, ceramic coating, Physical Vapor Deposition (PVD), Chemical Vapor Deposition (CVD), and Ion Assisted Coating (IAC).
  • PVD Physical Vapor Deposition
  • CVD Chemical Vapor Deposition
  • IAC Ion Assisted Coating
  • FIG. 1 is a scanning electron micrograph cross-sectional view of a representative carbide having a CVD coating thereon and prior to having titanium and nitride diffused therethrough in accordance with an aspect of the present invention
  • FIG. 2 is a cross-sectional view of a carbide treated with a CVD process and prior to having titanium and nitride diffused therethrough in accordance with an aspect of the present invention
  • FIG. 3 is a cross-sectional view of a carbide treated with a CVD process and after having titanium and nitride diffused therethrough in accordance with an aspect of the present invention.
  • FIG. 4 is a scanning electron micrograph cross-sectional view of a representative steel having a PVD coating thereon and prior to having titanium and nitride diffused therethrough in accordance with an aspect of the present invention.
  • the present invention involves a base material including a coating thereon.
  • the base material is defined herein as any material which requires hardness, tensile strength and/or resistance to wear.
  • Suitable base materials may include, but are not limited to, metals, metal alloys and/or carbides.
  • suitable base materials may further include, but are not limited to, aluminum, aluminum alloys, steel, steel alloys, titanium and titanium alloys.
  • the present invention also involves surface treatments and coatings.
  • surface treatments and coatings include any process which enhances the hardness, tensile strength and/or resistance to wear of a base material. Such processes include, but are not limited to, heat treatment, nanocoating, ceramic coating, Physical Vapor Deposition (PVD), Chemical Vapor Deposition (CVD), Ion Assisted Coating (IAC), and other suitable surface treatments or coatings.
  • PVD Physical Vapor Deposition
  • CVD Chemical Vapor Deposition
  • IAC Ion Assisted Coating
  • the base material may be treated with a conventional surface treatment or coating and then treated using the present invention titanium and nitride diffusion process.
  • the base material may be treated using the present invention titanium and nitride diffusion process and then treated with a conventional surface treatment or coating.
  • any conventional process for treating or coating materials may be used in these embodiments.
  • a base material may be treated with a conventional surface treatment or coating and then treated using the present invention titanium and nitride diffusion process as follows.
  • a base material is surface treated or coated using a suitable means. Otherwise, a base material having a coating thereon may be provided.
  • the base material having a coating thereon is soaked in a moderately heated non-electrolyzed salt bath which contains activated-electrolyzed metallic titanium.
  • Sodium dioxide and a salt selected from the group consisting of sodium cyanate and potassium cyanate is present in the salt bath. Additionally, up to about 20 w/w % of NaCO 2 or sodium chloride may further be added.
  • To the bath is added from about 2 to about 20 micrograms of electrolyzed metallic titanium.
  • the base material having a coating thereon is soaked in the bath for from about 10 minutes to 24 hours at from about 430° C. to about 670° C.
  • the electrolyzed titanium catalyzes the diffusion of the titanium and nitride from the bath into both the base material and the coating thereon.
  • titanium and nitrogen diffuses and fills the voids of the coating, while also diffusing and filling in the voids of the base material. Accordingly, both the base material and the coating are enhanced with inherent properties of titanium. Moreover, the diffusion from the coating en route to the underlying base material forms a resulting titanium interface or network therebetween. This interface or network provides for the added benefit of providing better adhesion between the coating and the underlying base material.
  • a treated article including a base material having a coating thereon, wherein the base material and coating each include a microstructure; a titanium component diffused into each of the microstructures; and the titanium component is in addition to any titanium present in each of the coating and the base material.
  • a treated article comprising a treated base material having a particular microstructure; a titanium component diffused into the microstructure; and the titanium component is in addition to any titanium present in the base material.
  • U.S. Pat. No. 6,645,566 describes soaking the base material from about 2 hours to about 10 hours, and preferably about 2 hours to about 6 hours. This soaking time is generally sufficient for ample diffusion of titanium and nitride into the amorphous structure of steel, aluminum and titanium. However and surprisingly, it is found that diffusion into the coating may occur as soon as 10 minutes into the soaking process. Furthermore, it is preferable to increase the time in which the base material having a coating thereon is soaked in the bath in order to facilitate adequate diffusion of titanium and nitride into both the coating and the base material.
  • FIGS. 1 and 2 illustrate base material 20 containing carbide having a CVD coating 22 thereon.
  • the base material 20 includes a generally compact, granular microstructure. Although the granular microstructure contributes to the hardness of the carbide, among the grains 23 are small voids 24 which perpetuate the brittleness of the carbide structure. In order to compensate for this brittleness, a coating may be formed thereon.
  • a CVD coating 22 is shown to be applied to the base material 20 using any conventional CVD process. More specifically, the base material may be exposed to one or more volatile precursors, which react and/or decompose on the base material to produce the desired coating 22 .
  • titanium carbo-nitride+alumina may be used (TiCN+Al 2 O 3 ).
  • titanium nitride+alumina+titanium carbo-nitride TiN+Al 2 O 3 +TiN
  • the coating 22 is shown to have a crystalline microstructure, wherein among the crystals 28 are small voids 30 . Like the voids 24 of the base material 20 , the voids 30 among the crystals 28 contribute to the brittleness of the coating 22 .
  • titanium and nitride may be diffused into and fill the voids 24 , 30 within both the base material 20 and the coating 22 as follows.
  • This base material 20 having a coating 22 thereon was treated by soaking in a heated salt bath (NaCNO and about 10 w/w % of NaCO 2 ), for 2 hours at 545° C. in which 2-20 micrograms of electrolyzed metallic titanium was added.
  • the base material 20 having a coating 22 thereon was then cooled and dried.
  • the base material 20 having a coating 22 thereon was then washed to remove an oxidation layer formed as a result of heat being applied thereto during and after the diffusion process.
  • titanium and nitride were diffused into both the coating 22 and the base material 20 as shown in FIG. 3 .
  • This diffusion was shown as the previously lighter material in FIG. 2 is now darker as shown in FIG. 3 .
  • the darkness appeared in both the coating 22 and the underlying carbide in the base material 20 . Accordingly, titanium and nitrogen diffused and filled the voids of the coating 22 , while also diffusing and filling in the voids among the grains of the carbide structure of the base material 20 .
  • Example 1 it is illustrated that titanium and nitride surprisingly diffuses into not only the base material, but also the coating thereon, using the process of the present invention.
  • a metal alloy comprising carbide was used as a base material for a turning insert.
  • the base material additionally included vanadium.
  • the turning insert was further treated with a CVD process. This turning insert was treated by soaking in a heated salt bath (NaCNO and about 10 w/w % of NaCO 2 ), for 2 hours at 545° C. in which 2-20 micrograms of electrolyzed metallic titanium was added. The turning insert was then cooled and dried. The insert was then washed to remove an oxidation layer formed as a result of heat being applied thereto during and after the diffusion process.
  • a heated salt bath NaCNO and about 10 w/w % of NaCO 2
  • the turning insert treated with the present invention process was surprisingly shown to have only slight wear.
  • the turning insert treated with only the CVD process showed significant chipping which resulted in catastrophic failure of the cutting tool.
  • a metal alloy comprising carbide was used as a base material for a turning insert.
  • the base material additionally included vanadium.
  • the turning insert was further treated with a CVD process. This turning insert was treated by soaking in a heated salt bath (NaCNO and about 10 w/w % of NaCO 2 ), for 2 hours at 545° C. in which 2-20 micrograms of electrolyzed metallic titanium was added. The turning insert was then cooled and dried. The insert was then washed to remove an oxidation layer formed as a result of heat being applied thereto during and after the diffusion process.
  • a heated salt bath NaCNO and about 10 w/w % of NaCO 2
  • the turning insert treated with the present invention process was surprisingly shown to have only slight wear.
  • the turning insert treated with only the CVD process showed significant chipping which resulted in catastrophic failure of the cutting tool.
  • FIG. 4 is a representative illustration of a base material including steel 40 having a PVD coating 42 thereon.
  • the base material 40 includes a generally amorphous microstructure. Within the amorphous microstructure are small voids 44 which decrease the hardness and tensile strength thereof. In order to compensate for such, a coating may be formed thereon.
  • a PVD coating 42 is shown to be applied to the base material 40 using any conventional PVD process. More specifically, a thin film (e.g., in this case coating 42 ) is applied to the base material 40 .
  • a thin film e.g., in this case coating 42
  • TiN titanium nitride
  • other suitable coatings may also be applied including, but not limited to titanium aluminum nitride (TiAlN), titanium carbo-nitride (TiCN) and chrome nitride (CrN) coatings.
  • the coating 42 is shown to have a generally crystalline microstructure, wherein among the crystals 46 are small voids 48 . Like the voids 44 of the base material 40 , the voids 48 among the crystals 46 contribute to decreased hardness and tensile strength of the coating 42 .
  • titanium and nitride may be diffused into and fill the voids 48 , 40 within both the base material 40 and the coating 42 as follows.
  • this base material was used in an end mill.
  • the end mill having the base material 40 and coating 42 thereon was treated by soaking in a heated salt bath (NaCNO and about 10 w/w % of NaCO 2 ), for 2 hours at 545° C. in which 2-20 micrograms of electrolyzed metallic titanium was added.
  • This end mill was then cooled and dried. The end mill was then washed to remove an oxidation layer formed as a result of heat being applied thereto during and after the diffusion process.
  • titanium and nitride were diffused into both the coating 42 and the base material 40 of the end mill. Moreover, the diffusion from the coating 42 en route to the underlying carbide in the base material 40 formed a resulting titanium interface or network therebetween. This interface or network provided for the added benefit of providing better adhesion between the coating 42 and the underlying base material 40 .
  • the base material may be treated using the present invention titanium and nitride diffusion process and then treated with a conventional surface treatment or coating as follows.
  • a base material is soaked in a moderately heated non-electrolyzed salt bath which contains activated-electrolyzed metallic titanium.
  • Sodium dioxide and a salt selected from the group consisting of sodium cyanate and potassium cyanate is present in the salt bath. Additionally, up to about 20 w/w % of NaCO 2 or sodium chloride may further be added.
  • To the bath is added from about 2 to about 20 micrograms of electrolyzed metallic titanium.
  • the base material is soaked in the bath for from about 10 minutes to 24 hours at from about 430° C. to about 670° C.
  • the electrolyzed titanium catalyzes the diffusion of the titanium and nitride from the bath into both the base material.
  • the base material which has been diffused with titanium and nitride may be further surface treated or coated using a suitable means such as heat treatment, nanocoating, ceramic coating, Physical Vapor Deposition (PVD), Chemical Vapor Deposition (CVD), Ion Assisted Coating (IAC), and other suitable surface treatments or coating.
  • a suitable means such as heat treatment, nanocoating, ceramic coating, Physical Vapor Deposition (PVD), Chemical Vapor Deposition (CVD), Ion Assisted Coating (IAC), and other suitable surface treatments or coating.
  • a hexagonal broach comprising a base material containing steel was provided.
  • the hexagonal broach was diffused with titanium and nitride and then further surface treated or coated as follows.
  • the hexagonal broach was treated by soaking in a heated salt bath (NaCNO and about 10 w/w % of NaCO 2 ), for 2 hours at 545° C. in which 2-20 micrograms of electrolyzed metallic titanium was added.
  • This hexagonal broach was then cooled and dried.
  • the tool was then washed to remove an oxidation layer formed as a result of heat being applied thereto during and after the diffusion process. Through this process, titanium and nitride diffused into the base material of the tool.
  • the treated hexagonal broach was further treated using a conventional PVD process. More specifically, a thin film of TiN coating was applied to the surface of treated hexagonal broach.
  • the aforementioned hexagonal broach treated with the present invention process was tested and compared to a hexagonal broach having a TiN coating applied using the same conventional PVD process under the same operating parameters. More specifically, the broaches were used to machine the same type of titanium part under the same operating parameters. It was observed that the broach treated in accordance with the present invention was able to machine 1950 parts. In contrast, the broach treated with only a conventional PVD process was only able to machine 1100 parts.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Physical Vapour Deposition (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
US11/405,959 2006-04-18 2006-04-18 Process for diffusing titanium and nitride into a material having a coating thereon Expired - Fee Related US7438769B2 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
US11/405,959 US7438769B2 (en) 2006-04-18 2006-04-18 Process for diffusing titanium and nitride into a material having a coating thereon
CN201310140402.7A CN103215539B (zh) 2006-04-18 2007-04-10 将钛和氮化物扩散到经涂布材料中的方法
KR1020147003959A KR101496686B1 (ko) 2006-04-18 2007-04-10 코팅된 재료 내로 티탄 및 질화물을 확산시키는 방법
JP2009506686A JP2009534534A (ja) 2006-04-18 2007-04-10 被覆体をもつ材料にチタンおよび窒化物を拡散する方法、およびこの方法によって製造した製品
BRPI0710618-1A BRPI0710618A2 (pt) 2006-04-18 2007-04-10 método para difundir titánio e nitreto em um material base e artigo tratado
MX2008013364A MX2008013364A (es) 2006-04-18 2007-04-10 Proceso para difundir titanio y nitruro en un material que tiene un recubrimiento en el mismo y los productos producidos por el mismo.
EP07760366A EP2007572A4 (fr) 2006-04-18 2007-04-10 Procédé de diffusion de titane et de nitrure dans un matériau revêtu, et produits ainsi obtenus
CN2007800226294A CN101535038B (zh) 2006-04-18 2007-04-10 将钛和氮化物扩散到经涂布材料中的方法
KR1020087028059A KR20090068190A (ko) 2006-04-18 2007-04-10 코팅된 재료 내로 티탄 및 질화물을 확산시키는 방법
PCT/US2007/066291 WO2007121157A2 (fr) 2006-04-18 2007-04-10 Procédé de diffusion de titane et de nitrure dans un matériau revêtu, et produits ainsi obtenus
CA002649232A CA2649232A1 (fr) 2006-04-18 2007-04-10 Procede de diffusion de titane et de nitrure dans un materiau revetu, et produits ainsi obtenus
US12/251,617 US20090035481A1 (en) 2006-04-18 2008-10-15 Process for diffusing titanium and nitride into a material having a coating thereon and products produced thereby

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US11/405,959 US7438769B2 (en) 2006-04-18 2006-04-18 Process for diffusing titanium and nitride into a material having a coating thereon

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/251,617 Continuation US20090035481A1 (en) 2006-04-18 2008-10-15 Process for diffusing titanium and nitride into a material having a coating thereon and products produced thereby

Publications (2)

Publication Number Publication Date
US20070243398A1 US20070243398A1 (en) 2007-10-18
US7438769B2 true US7438769B2 (en) 2008-10-21

Family

ID=38605174

Family Applications (2)

Application Number Title Priority Date Filing Date
US11/405,959 Expired - Fee Related US7438769B2 (en) 2006-04-18 2006-04-18 Process for diffusing titanium and nitride into a material having a coating thereon
US12/251,617 Abandoned US20090035481A1 (en) 2006-04-18 2008-10-15 Process for diffusing titanium and nitride into a material having a coating thereon and products produced thereby

Family Applications After (1)

Application Number Title Priority Date Filing Date
US12/251,617 Abandoned US20090035481A1 (en) 2006-04-18 2008-10-15 Process for diffusing titanium and nitride into a material having a coating thereon and products produced thereby

Country Status (9)

Country Link
US (2) US7438769B2 (fr)
EP (1) EP2007572A4 (fr)
JP (1) JP2009534534A (fr)
KR (2) KR20090068190A (fr)
CN (2) CN101535038B (fr)
BR (1) BRPI0710618A2 (fr)
CA (1) CA2649232A1 (fr)
MX (1) MX2008013364A (fr)
WO (1) WO2007121157A2 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070243412A1 (en) * 2006-04-18 2007-10-18 Ko Philos J Process for diffusing titanium and nitride into a material having a generally compact, granular microstructure and products produced thereby
US20090035481A1 (en) * 2006-04-18 2009-02-05 Philos Jongho Ko Process for diffusing titanium and nitride into a material having a coating thereon and products produced thereby
US20100299931A1 (en) * 2009-05-26 2010-12-02 Krassimir Grigorov Marchev Strengthened razor blade
US20120244385A1 (en) * 2011-03-24 2012-09-27 Hon Hai Precision Industry Co., Ltd. Metal housing and surface treating method thereof
US20140141277A1 (en) * 2011-06-03 2014-05-22 Frederick Goldman, Inc. Coated metallic products and methods for making the same

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101987396B (zh) * 2009-07-31 2014-02-19 鸿富锦精密工业（深圳）有限公司 锆基块体非晶合金激光焊接方法及焊接结构
CN101831604B (zh) * 2010-06-01 2012-01-25 成都伍田机械技术有限责任公司 用于液体氮化的氮化盐
CN102719786A (zh) * 2011-03-29 2012-10-10 鸿富锦精密工业（深圳）有限公司 金属壳体及其表面处理方法
US10902749B2 (en) 2011-06-21 2021-01-26 Polymeric Converting Llc Self sealing tag stock
CN102492918B (zh) * 2011-11-29 2013-10-30 青岛张氏机械有限公司 活塞杆、活塞杆表面处理的碳氮共渗剂及其生产方法
EP2844465A4 (fr) * 2012-05-04 2016-06-29 Philos Jongho Ko Procédé perfectionné pour diffuser un substrat dans une matière de base
CN102965613B (zh) * 2012-12-05 2014-10-15 南京航空航天大学 一种钛合金低温表面渗氮方法
DE102015111993A1 (de) * 2015-07-23 2017-01-26 Schott Ag Formdorn mit Diffusionsschicht zur Glasformung
CN110230024B (zh) * 2018-12-14 2021-08-13 昆山三民涂赖电子材料技术有限公司 用于对金属表面渗氮化的工艺
CN110230023B (zh) * 2018-12-14 2021-07-16 常德市广和机械制造有限公司 金属表面盐浴氮化及qpq工艺
CN110230022B (zh) * 2018-12-14 2021-08-13 昆山三民涂赖电子材料技术有限公司 用于对金属表面处理的qpq工艺
KR102375231B1 (ko) * 2020-09-10 2022-03-15 조영대 금속 모재의 질화 열처리 방법

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3639641A (en) 1965-08-31 1972-02-01 Shinzoh Satoh Method for rapid manufacture of nitrided thick layer of super high hardness on ferrous metal articles
US4019928A (en) 1973-03-05 1977-04-26 Duetsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for nitriding iron and steel in salt baths regenerated with triazine polymers
US4332653A (en) 1980-06-13 1982-06-01 Shinzoh Satoh Method of nitriding by high temperature electrolysis
US4492604A (en) 1981-10-24 1985-01-08 Degussa Aktiengesellschaft Salt bath for nitriding iron materials
US6645566B2 (en) 1999-06-01 2003-11-11 Jong Ho Ko Process for heat treatment nitriding in the presence of titanium and products produced thereby
US6881498B1 (en) * 2004-06-24 2005-04-19 Sikorsky Aircraft Corporation Surface process involving isotropic superfinishing

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85100311B (zh) * 1985-04-01 1986-12-17 沈阳机电学院 硼-稀土-硅三元共渗盐浴成分
JP2977105B2 (ja) * 1992-03-12 1999-11-10 マツダ株式会社 耐摩耗性に優れた摺動部材の製造方法
CN1025440C (zh) * 1992-04-08 1994-07-13 机械电子工业部武汉材料保护研究所 钢铁低温盐浴钒氮共渗表面改性工艺
CN1031950C (zh) * 1993-03-19 1996-06-05 福建省冶金工业研究所 盐浴稀土钒硼共渗工艺
KR100513563B1 (ko) * 2002-05-21 2005-09-09 고종호 티탄 존재 하에서의 금속 모재의 질화 열처리방법
US7438769B2 (en) * 2006-04-18 2008-10-21 Philos Jongho Ko Process for diffusing titanium and nitride into a material having a coating thereon
KR20090113244A (ko) * 2006-10-06 2009-10-29 필로스 종호 고 함량을 변화시켜 티타늄 및 질화물의 강철 또는 강철 합금으로의 확산을 개선한 방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3639641A (en) 1965-08-31 1972-02-01 Shinzoh Satoh Method for rapid manufacture of nitrided thick layer of super high hardness on ferrous metal articles
US4019928A (en) 1973-03-05 1977-04-26 Duetsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for nitriding iron and steel in salt baths regenerated with triazine polymers
US4332653A (en) 1980-06-13 1982-06-01 Shinzoh Satoh Method of nitriding by high temperature electrolysis
US4492604A (en) 1981-10-24 1985-01-08 Degussa Aktiengesellschaft Salt bath for nitriding iron materials
US6645566B2 (en) 1999-06-01 2003-11-11 Jong Ho Ko Process for heat treatment nitriding in the presence of titanium and products produced thereby
US6881498B1 (en) * 2004-06-24 2005-04-19 Sikorsky Aircraft Corporation Surface process involving isotropic superfinishing

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070243412A1 (en) * 2006-04-18 2007-10-18 Ko Philos J Process for diffusing titanium and nitride into a material having a generally compact, granular microstructure and products produced thereby
US20090035481A1 (en) * 2006-04-18 2009-02-05 Philos Jongho Ko Process for diffusing titanium and nitride into a material having a coating thereon and products produced thereby
US7732014B2 (en) * 2006-04-18 2010-06-08 Philos Jongho Ko Process for diffusing titanium and nitride into a material having a generally compact, granular microstructure
US20100299931A1 (en) * 2009-05-26 2010-12-02 Krassimir Grigorov Marchev Strengthened razor blade
US9598761B2 (en) 2009-05-26 2017-03-21 The Gillette Company Strengthened razor blade
US9855665B2 (en) 2009-05-26 2018-01-02 The Gillette Company Llc Strengthened razor blade
US20120244385A1 (en) * 2011-03-24 2012-09-27 Hon Hai Precision Industry Co., Ltd. Metal housing and surface treating method thereof
US20140141277A1 (en) * 2011-06-03 2014-05-22 Frederick Goldman, Inc. Coated metallic products and methods for making the same
US9034488B2 (en) * 2011-06-03 2015-05-19 Frederick Goldman, Inc. Coated metallic products and methods for making the same
US9629425B2 (en) 2011-06-03 2017-04-25 Frederick Goldman, Inc. Coated metallic products and methods for making the same

Also Published As

Publication number Publication date
CA2649232A1 (fr) 2007-10-25
US20090035481A1 (en) 2009-02-05
KR101496686B1 (ko) 2015-03-02
EP2007572A4 (fr) 2012-06-06
CN103215539B (zh) 2016-10-05
CN101535038B (zh) 2013-05-29
BRPI0710618A2 (pt) 2011-08-16
EP2007572A2 (fr) 2008-12-31
CN101535038A (zh) 2009-09-16
WO2007121157A2 (fr) 2007-10-25
JP2009534534A (ja) 2009-09-24
KR20090068190A (ko) 2009-06-25
US20070243398A1 (en) 2007-10-18
MX2008013364A (es) 2009-04-15
WO2007121157A3 (fr) 2007-12-13
CN103215539A (zh) 2013-07-24
KR20140029544A (ko) 2014-03-10

Similar Documents

Publication Publication Date Title
US7438769B2 (en) Process for diffusing titanium and nitride into a material having a coating thereon
EP2053144A1 (fr) Procédé de trempe d'une pièce en acier, pièce en acier trempée et agent de protection de surface trempée
US6090223A (en) Chromium nitride film and method for forming the same
Zimmerman Boriding (boronizing) of Metals
US8092915B2 (en) Products produced by a process for diffusing titanium and nitride into a material having generally compact, granular microstructure
US20100037991A1 (en) Diffusion promoters for low temperature case hardening
JP2773092B2 (ja) 表面被覆鋼製品
US20100154938A1 (en) Layered fe-based alloy and process for production thereof
CA1304658C (fr) Methode de traitement superficiel d'un objet en fer ou en alliage de fer
US20080226831A1 (en) process for diffusing titanium and nitride into a steel or steel alloy by altering the content of such
JP3779949B2 (ja) 硬質皮膜被覆工具
JP3779948B2 (ja) 硬質皮膜被覆工具
RU2386726C1 (ru) Способ упрочнения поверхностей стальных поршневых колец
WO2007015514A1 (fr) ALLIAGE STRATIFIÉ À BASE DE Fe ET PROCÉDÉ DE PRODUCTION
JP3679076B2 (ja) 硬質皮膜被覆工具
JP2009035761A (ja) 高硬度、耐摩耗性部品およびその製造方法
Matijević et al. Application of vanadizing process for tools and dies
TR201911356A2 (tr) Macunlu borürleme i̇çi̇n bi̇r yöntem
JP4494995B2 (ja) 金属材表面処理方法
JP3779951B2 (ja) 硬質皮膜被覆工具
JPH1128622A (ja) 表面改質方法及び表面改質工具

Legal Events

Date Code Title Description
REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20121021